Electrochimica Acta最新文献

{"title":"Effect of specific electrochemical settings and anion types on titanium oxide layer properties after anodization in near-neutral electrolytes for dental applications","authors":"Kedar Mehta, Friederike Kaiser, Philipp Stahlhut, Cornelia Wolf-Brandstetter","doi":"10.1016/j.electacta.2025.147405","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.147405","url":null,"abstract":"The effect of anodically formed oxide layer on titanium using different anion namely phosphate, acetate, sulfate, iodide, and thiocyanate containing electrolytes on the corrosion resistance and electrochemical behavior in artificial saliva (AS) was investigated at physiological temperature 37°C, using open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. We also evaluated the impact of anodization parameters specifically applied voltage and current density on these oxide films. The galvanostatic growth of anodic oxide films on titanium can be accompanied by the incorporation of species from the electrolyte into the oxide, affecting the properties of the final oxide. OCP was shifted to less negative values for all anodized Ti compared to polished Ti. The thickness of the oxide layer was dependent on the oxidation potential. Titanium anodized with phosphate and acetate reflected robust and stable oxide layer showing consistent performance. Higher corrosion current density was measured for oxide prepared with sulfate and thiocyanate electrolytes, especially for oxide layer prepared up to 10 V_SCE. When TiO₂ is prepared up to 10 V_SCE, no distinct porous layer resistance (R_p) appears and the barrier layer resistance (R_b) dominates, indicating a compact oxide. TiO₂ shows both R_p and R_b, indicating a dual-layer structure with a porous outer layer and a dense barrier layer beneath when prepared up to 90 V_SCE, both R_p and R_b are present, showing a dual‐layer structure with a porous top layer and a dense barrier beneath. Regardless of the anion, all electrolytes produced strong barrier layers with R_b values exceeding those of the polished reference. After 14 days’ incubation in AS, all anodized titanium samples exhibited significantly higher OCP and corrosion potentials than polished titanium, indicating greater electrochemical stability across formation voltages and current densities. A voltage of 10 V_SCE already generated compact and protective barrier layers, with slightly better stability at higher current density (25 mA/cm²). In contrast, 90 V_SCE produced thicker two-layer oxides, but these did not consistently outperform the compact films formed at 10 V_SCE.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"66 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145067806","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fabrication and Characterization of Copper Micropillars with Hydrophobic Surfaces via Light-Induced Electrodeposition","authors":"Zibo Di, Chenghan Zhao, Wenzheng Wu","doi":"10.1016/j.electacta.2025.147402","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.147402","url":null,"abstract":"A light-induced electrodeposition system was developed to study the fabrication of copper micropillars. The effects of electrode gap and hydrogenated amorphous silicon (a-Si:H) thickness were systematically investigated. The results show that the electrode gap strongly influences pillar morphology, deposition rate, and diameter. An appropriate gap leads to dense and uniform microstructures, as confirmed by cross-sectional analysis. The thickness of the a-Si:H layer also plays a key role: thicker layers enhance deposition efficiency, improve structural uniformity, and increase surface hydrophobicity. Using this approach, copper surfaces with micro/nanostructures and strong hydrophobic properties were successfully fabricated, providing a potential strategy for functional surface design in microscale applications.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"15 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145067737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Validated multiphysics simulation of die-scale co-planarity and mass transport limitations in copper pillar electroplating","authors":"Yu-Cheng Kuo ,&nbsp;Shih-Hao Huang ,&nbsp;Che-Yi Huang ,&nbsp;Hiew-Watt NG ,&nbsp;Hong-Kang Tian","doi":"10.1016/j.electacta.2025.147403","DOIUrl":"10.1016/j.electacta.2025.147403","url":null,"abstract":"<div><div>In advanced wafer-level packaging, achieving co-planarity of copper (Cu) pillars is essential for device yield and reliability, yet remains challenging due to non-uniform current distribution and localized mass transport limitations during electroplating. We present an experimentally validated, computationally efficient simulation strategy that couples multi-physics modeling of fluid dynamics, mass transport, and Butler–Volmer kinetics with a novel geometric approximation, enabling full die-scale predictions at a fraction of the computational cost of direct modeling. Complex layouts are partitioned into an <em>N</em> × <em>N</em> grid, with dense bump regions represented as equivalent circular electrodes, allowing accurate resolution of local current density and Cu²⁺ depletion effects. Across multiple layouts, simulated maximum and minimum bump heights deviate from experimental measurements by &lt;1.5 %, confirming the model’s predictive capability. Analysis reveals that non-uniformity is driven by a spatially dependent transition from kinetic control to mass-transport control in densely patterned regions. Requiring only layout geometry as input, the method provides a practical tool for early-stage design screening and process optimization, reducing costly experimental iterations in advanced packaging development.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"542 ","pages":"Article 147403"},"PeriodicalIF":5.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145072187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual-Nitrogen Coordination Shell Engineering in o-B2N2 Monolayer Supported Dual-Atom Catalysts for Oxygen Reduction Reaction","authors":"Yukai Dong, Weiye Li, Yuanbiao Liu, Zihan Wang, Chaochao Cao, Weimeng Si, Jun Cao, Fang Liu, Shanshan Xu, Qiaoling Li","doi":"10.1016/j.electacta.2025.147399","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.147399","url":null,"abstract":"Single-atom and dual-atom catalysts (SACs/DACs) have emerged as promising candidates for the oxygen reduction reaction (ORR), but it is still challenging due to the absence of robust substrates for simultaneously addressing the structure stability and activity issues. Herein, by using density functional theory (DFT) computations, a novel two-dimensional orthorhombic diboron dinitride (o-B₂N₂) monolayer with a narrow bandgap (0.66 eV) was developed and evaluated as an electrocatalyst substrate for ORR. A synergistic strategy involving dual transition metal atoms coordinated within a dual-nitrogen shell (TM-N-N) was employed to optimize the ORR performance. Remarkably, all TM₂@o-B₂N₂ monolayers based on 3d transition metals exhibit excellent thermal and electrochemical stability. Additionally, a di-iron centered o-B₂N₂ (Fe₂@o-B₂N₂) was identified among a series of TM₂@o-B₂N₂ monolayers, exhibiting superior ORR performance. The electrocatalytic activity was probed via crystal orbital Hamilton population (COHP), differential charge density, and molecular orbital analyses, revealing the electronic origins of the enhanced performance. The enhanced ORR activity of Fe₂@o-B₂N₂ originates from strong Fe-3d/N-2p orbital hybridization in the Fe-N-N coordination shell. The dual-nitrogen layer and di-metal sites synergistically modulate the d-band center, optimizing the adsorption of key species (e.g., *O₂/*OH) by facilitating electron redistribution from antibonding to bonding states, surpassing traditional h-BN and N-doped graphene counterparts. This work not only establishes Fe₂@o-B₂N₂ as an excellent ORR electrocatalyst, but also unveils a novel BN-like substrate material with broad applicability in electrocatalytic systems.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"38 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145067740","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Suppressing dendrite growth of the cadmium deposits in a high-viscous ethylene glycol solution by pulse electrodeposition","authors":"Yu Wu, Lixi Tian, Chunxia Wang, Xiao Luo, Kaishan Lin, Jiajia Xiang, Jinhui Dai","doi":"10.1016/j.electacta.2025.147404","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.147404","url":null,"abstract":"Electrodepositing cadmium in the non-aqueous ethylene glycol solution eliminates the risk of hydrogen embrittlement. However, the high viscosity of ethylene glycol combined with the large ionic radius of cadmium ions leads to significant concentration polarization, resulting in the formation of porous deposits and dendritic growth at the substrate edges. This study employed pulse electrodeposition and compared the effects of different current waveforms (direct current, unidirectional pulse current, and direct current superimposed with bidirectional pulse current) to address these issues. The results demonstrate that pulse currents significantly enhance the nucleation rate during the initial deposition stage, thereby substantially improving the compactness of the coatings. Introducing bidirectional pulse currents onto a DC baseline effectively suppresses dendritic growth at the edges and increases the effective coating thickness. This beneficial effect is achieved through the preferential dissolution of edge dendrites by the anodic current pulses, which weakens the concentration polarization effect. A detailed discussion on the nucleation and growth processes of the deposits under different current waveforms is provided. This work offers a feasible pathway for electrodepositing high-performance, corrosion-resistant coatings in high-viscosity systems.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"77 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145067735","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-Efficiency Electrocatalytic Splitting of water/seawater Enabled by Ni3S2 Nanosheets Anchored on Amorphous Ni,Fe-OH with Enhanced Electron Transfer","authors":"Haiyu Wang, Chenchen Feng, Bo Huang, Baoning Li, Jian Li, Zhiliang Jin, Long Yan, Yufei Wang","doi":"10.1016/j.electacta.2025.147397","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.147397","url":null,"abstract":"Water electrolysis holds significant potential for advancing the establishment of a viable green hydrogen ecosystem. However, its widespread industrial application is severely hindered by the sluggish kinetics of catalytic reactions. Enhancing the electron transfer efficiency of electrocatalysts is crucial for accelerating the kinetics of the oxygen evolution reaction (OER). To address this, a heterojunction catalyst composed of Ni₃S₂ nanosheets anchored on an amorphous Ni,Fe-OH surface was fabricated on nickel foam (NF). The Ni₃S₂/Ni,Fe-OH catalyst exhibits an exceptionally low Tafel slope (65.3 mV dec^-1) and an overpotential of 412 mV at 500 mA cm⁻². Moreover, it demonstrates outstanding long-term stability across a wide current density range of 0.05-2 A cm⁻², in both water and simulated seawater splitting. Density functional theory (DFT) calculations reveal that the higher partial density of states (PDOS) of the Ni₃S₂ catalyst facilitates accelerated electron transfer to the amorphous Ni,Fe-OH. Mechanism study identifies NiOOH as the active intermediate during the OER process. This research highlights the considerable promise of heterojunctions formed between crystalline and amorphous structures in catalysts for water and seawater electrolysis.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"17 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145067742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comparison of solvation behavior and ionic conductance of A-site Sr and Ca doped and B-site Cu doped LaAlO3","authors":"Jie Yang, Rui Zhou, Jinlei Meng, Jingchen Sun","doi":"10.1016/j.electacta.2025.147401","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.147401","url":null,"abstract":"Enhancing ionic conductivity while reducing the sintering temperature remains a critical challenge in solid oxide fuel cell (SOFC) research. In this study, we first employed Cu doping at the B-site to lower the sintering temperature and identify an optimal doping ratio of 10 mol% LaAl_0.9Cu_0.1O_3-δ(LAC10). Density functional theory (DFT) calculations further indicate that LAC10 exhibits favorable ionic conduction characteristics. Building upon this Cu-doped matrix, we systematically investigated the effects of A-site substitution with divalent cations (Ca²⁺, Sr²⁺) on microstructure and electrochemical performance. Compared to undoped LaAlO₃ (9.82 * 10^-6 S·cm⁻¹) and Cu-only LAC10 (1.05 * 10^-2 S·cm⁻¹), the La_0.8Sr_0.2Al_0.9Cu_0.1O_3-δ composition demonstrates significantly enhanced ionic conductivity (1.44 * 10^-2 S·cm⁻¹) and a relatively low activation energy of 0.481 eV. Moreover, a single cell employing this electrolyte achieved a peak power density of 611.76 mW·cm⁻² at 700°C. These results demonstrate that the combined incorporation of Sr and Cu into the LaAlO₃ lattice substantially improves SOFC-relevant properties, making La_0.8Sr_0.2Al_0.9Cu_0.1O_3-δ a promising electrolyte candidate.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"36 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145072189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Degradation mechanisms of a proton exchange membrane water electrolyzer stack operating at high current densities","authors":"Benjamin Kimmel ,&nbsp;Tobias Morawietz ,&nbsp;Pawel Gazdzicki ,&nbsp;Aldo S. Gago ,&nbsp;K. Andreas Friedrich","doi":"10.1016/j.electacta.2025.147395","DOIUrl":"10.1016/j.electacta.2025.147395","url":null,"abstract":"<div><div>On the path to an emission free energy economy, proton exchange membrane water electrolysis (PEMWE) is a promising technology for a sustainable production of green hydrogen at high current densities and thus high production rates. Long lifetime, increasing the current density and the reduction of platinum group metal loadings are major challenges for a widespread implementation of PEMWE. In this context, this work investigates the aging of a PEMWE stack operating at 4 A cm^-2, which is twice the nominal current density of commercial electrolyzers. Specifically, an 8-cells PEMWE stack using catalyst coated membranes (CCMs) with different platinum group metal (PGM) loading was operated for 2200 h. To understand degradation phenomena, physical ex-situ analyses, such as scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS), were carried out. The same aging mechanism were observed in all cells, independent on their position in stack or the specific PGM loading of the membrane electrode assembly (CCM): (i) a decrease of ohmic resistance over time related to membrane thinning, (ii) a significant loss of ionomer at anodes, (iii) loss of noble metal from the electrodes leading to deposition of small Ir and Pt concentrations in the membrane, (iv) heterogeneous enrichment of Ti on the cathode side likely originating from the cathode-side of the Ti bipolar plates (BPPs). These results are in good agreement with the electrochemical performance loss. Thus, we were able to identify the degradation phenomena that dominate under high-current operation and their impact on performance.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"542 ","pages":"Article 147395"},"PeriodicalIF":5.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145067802","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In-situ Construction and Performance Study of ZnCu-ZIF Zinc Anode Protective Layer","authors":"Yaya Wang, Yunhua Gu, Fengcui Shen, Chao Yang, Xinrui Ren, Rongmei Liu","doi":"10.1016/j.electacta.2025.147391","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.147391","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) have garnered significant attention owing to their merits of high safety, high theoretical specific capacity, low cost, and environmental benignity. However, irreversible challenges posed by side reactions and dendrite growth on zinc anodes have impeded their commercial deployment in large-scale energy storage applications. In this paper, a ZnCu-ZIF protective layer was in-situ grown on Zn foil through simple redox and coordination reactions to address the above issues. The protective layer efficiently isolates the anode surface from the aqueous electrolyte, thereby curbing severe parasitic reactions. Additionally, it facilitates uniform Zn deposition and mitigates dendrite growth. The findings indicate that the ZnCu-ZIF@Zn-1h symmetric cell maintains stable cycling for 2600 hours at 1 mA cm⁻² and 1 mAh cm⁻², demonstrating exceptional cycle stability. In addition, the ZnCu-ZIF@Zn-1h||MnO₂ full cell has a high specific capacity of 285.6 mAh g⁻¹ at 0.1 A g⁻¹ and demonstrates excellent rate performance. Meanwhile, it retains 82.9% of its initial capacity after 1000 cycles at 1 A g⁻¹, exemplifying outstanding electrochemical durability. This work thus provides a novel paradigm for the facile scalable fabrication of highly reversible Zn metal anodes, highlighting significant potential for practical implementation.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"72 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical pathway-controlled growth of tellurium nanostructures on a nonconductive substrate","authors":"Jinmyeong Seo ,&nbsp;Jungjoon Park ,&nbsp;Haneul Han ,&nbsp;Soojin Kim ,&nbsp;Soobin Park ,&nbsp;Sanghwa Yoon ,&nbsp;Bongyoung Yoo","doi":"10.1016/j.electacta.2025.147390","DOIUrl":"10.1016/j.electacta.2025.147390","url":null,"abstract":"<div><div>This study demonstrates that the morphology and spatial distribution of tellurium (Te) nanostructures can be precisely controlled on electrically insulating substrates (SiO₂) by systematically tuning the electrochemical reaction pathway of HTeO₂⁺. By varying only two key parameters, the precursor concentration and applied potential, the relative contribution of each step, including the overpotential deposition, H₂Te formation, and chemical reduction, was modulated. This enabled the fabrication of diverse nanostructures, including nano-dots, nano-rods, and feather-like morphologies, under different electrochemical conditions. Notably, Te formation was achieved solely via the chemical pathway on insulating SiO₂ without the need for external electron transport, providing the first unambiguous experimental validation of EC-driven formation and growth on electrically insulating substrate. This strategy successfully circumvents the limitations of conventional electroplating techniques, which are generally restricted to conductive substrates, and offers a template-free platform for the site- and shape-selective growth of Te nanostructures. These findings present a promising route toward applications in Te-based sensors, thermoelectric devices, and bio-functional nanomaterials.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"541 ","pages":"Article 147390"},"PeriodicalIF":5.6,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}